CN1830548A - Preparation method of mesopore titanium oxide whisker shaping material - Google Patents
Preparation method of mesopore titanium oxide whisker shaping material Download PDFInfo
- Publication number
- CN1830548A CN1830548A CN 200610038863 CN200610038863A CN1830548A CN 1830548 A CN1830548 A CN 1830548A CN 200610038863 CN200610038863 CN 200610038863 CN 200610038863 A CN200610038863 A CN 200610038863A CN 1830548 A CN1830548 A CN 1830548A
- Authority
- CN
- China
- Prior art keywords
- titanium oxide
- preparation
- whisker
- potassium
- meso
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A process for preparing the shaped meso-porous titanium oxide whisker material includes such steps as providing the meso-porous titanium oxide whisker and one or more of potassium titanate or its derivative and other kinds of titanium oxide, shaping and calcining. It has high crystallized degree (more than 20%), regularly ordered nano structure, 30-180 sq.m/g for specific surface area, 0.4-3 MPa for breaking strength, 30-80% for porosity and 0.1-0.7 cu.m/g for pore volume.
Description
Technical field
The invention belongs to the preparing technical field of catalyst material, specifically for not containing other moulding additives, high-crystallinity, having the preparation method of the mesopore titanium oxide whisker shaping material of regular nanostructured, bigger serface, high crushing strength, porous profile.
Background technology
General catalyst all is made up of carrier and active metal component, and the catalysis material of preparing carrier and catalyst double action has tempting industrial prospect because of reducing production costs greatly.γ-Al
2O
3Have characteristics such as high-specific surface area, high strength, but, can not improve reactivity as inert carrier; Though the MCM-41 mesopore molecular sieve has high-specific surface area, regular ordered big hole, strong acid center and poor chemical stability are easily stopped up, do not had in its duct; The TS molecular sieve generally will be with a large amount of template agent in preparation process, and structural stability is poor.
Nano-TiO
2Have good catalytic performance, but be difficult to recovery and reuse.In order to overcome above shortcoming, generally be prepared into thin film of titanium oxide, but since not high in the carrier surface tack, in course of reaction, can cause catalyst loss.General T iO
2Particle or whisker moulding have also obtained broad research, but have some weakness always, and be less relatively as specific area
[1], active Detitanium-ore-type is at high temperature stable inadequately, bad mechanical strength
[2], its industrialization is restricted.The titanium oxide of preparation high-specific surface area is mainly by sol-gel process, but because the process complexity, expensive raw material price etc. and can not industrialization.In order to improve TiO
2The mechanical performance of carrier generally is to add various additives or improve sintering temperature in forming process.Inorganic binder
[3-6]Can improve intensity and heat endurance with the adding of sintering aid, but these inorganic additives can become impurity and influence catalytic performance greatly; Add organic additive such as acetate
[7], organic amine
[8]After can change the surface nature of titanium oxide.Sintering temperature is high more, and specific area descends obvious more
[9]General titanium oxide calcining matter only is tens m
2/ g even littler, and undergone phase transition.Catalyst crystallization degree and micro-structural have a significant impact reaction, and degree of crystallinity is high more, and crystal is complete more, and catalytic activity is high more.In general, anatase phase oxidation titanium is higher than the catalytic performance of rutile phase; Simultaneously, the porosity reduction that reduces the surface-active bit quantity cause will cause reactive activity and speed to reduce greatly; Studies show that porous profile activity of such catalysts and reaction rate are higher 3～8 times than single hole profile catalyst.After being supported on the moulding titanium oxide with commonsense method, alkali metal ion runs off easily and makes catalyst activity reduction.
Summary of the invention
The objective of the invention is to prepare a kind of high-crystallinity, have regular nanostructured, bigger serface, high crushing strength, porous profile, do not contain the mesopore titanium oxide whisker shaping material of other moulding additives.
Purpose of the present invention can reach by following measure:
The meso-porous titanium oxide whisker that the present invention uses has the regular nano-pore structure of 4 ~ 10nm
[10], when keeping high-specific surface area, high-crystallinity is arranged again, in catalytic reactions such as light degradation organic matter and phenol hydroxylation, show superior performance.It is to be raw material with titanium compound and potassium compound according to the patent No. (ZL03158274.5), and the raw material titanium compound is amounted to into TiO with potassium compound
2With K
2O presses TiO
2/ K
2O=1～4mol ratio mixes, and obtains the product potassium titanate more than 30 minutes at 600～1100 ℃ of sintering, wherein contains two potassium titanate crystal; It is characterized in that sintered product disperses in water after, place 20～100 ℃, 1～50 times pH 〉=8 alkaline solution or contain＞K of 1mol/L
+Reaction is more than 4 hours in the solution, hydration-treated in the acid solution of pH＜5 then, and the potassium content of the hydrated product that obtains is less than the 5wt% of product weight, and specific area is greater than 100m
2/ g; This product dewaters through heat treatment method, can crystallization becomes hydrous titanium oxide, eight metatitanic acids, monocline type titanium dioxide, anatase titanium dioxide, rutile titanium dioxide or above-mentioned more than one titania mixture, and its specific area is greater than 50m
2/ g, form is diameter or the equivalent diameter whisker at 0.1～10 μ m.And the potassium titanate or derivatives thereof that adds in the meso-porous titanium oxide whisker is a kind of solid base, in course of reaction by ion-exchange
[11]Deng the constantly slow stripping K of reaction
+, the Acidity of Aikalinity of regulator solution makes a certain condition of remaining on of reaction system long-term stability, promotes the carrying out of reaction.Titania precursor body such as the titanium oxide sol that adds in moulding material, metatitanic acid, hydrous titanium oxide or anatase titanium oxide particle or whisker be generally as binding agent, and can not cause catalytic activity to descend when improving the moulding material crushing strength.Therefore, the moulding material of the present invention preparation can be used as efficient preformed catalyst again and is used for catalytic reaction when playing the general carrier effect.
The present invention is a raw material with one or more mixture and the meso-porous titanium oxide whisker in potassium titanate or derivatives thereof or other titanium oxide, makes after moulding, 300 ℃～700 ℃ roastings, and meso-porous titanium oxide whisker weight percent content is 5～80.
Purpose of the present invention can also reach by following measure:
Moulding material degree of crystallinity＞20%, specific area are 30～180m
2/ g, crushing strength is 0.4～3MPa, and porosity is 30～80%, and pore volume is 0.1～0.7cm
3/ g has at least two kinds in following three kinds of aperture features distributions, and first feature is distributed as 4～10nm, and second feature is distributed as 10～100nm, and the 3rd feature is distributed as 0.1～10 μ m;
Its equivalent diameter of moulding material is greater than 0.2mm;
Potassium titanate is one or more the mixture in two potassium titanates, potassium tetratitanate, six potassium titanates, eight potassium titanate particles or the whisker;
The potassium titanate derivative is the potassium titanate that contains after the crystallization water or the ion-exchange;
Other titanium oxide are one or more the mixture in the amorphous compound of Detitanium-ore-type phase oxidation titanium whisker or particle or titanium;
The amorphous compound of titanium is by the titanium oxide of sol-gel preparation or one or more the mixture in metatitanic acid or the hydrolysis oxidation titanium;
The specific area of meso-porous titanium oxide whisker is greater than 50m
2/ g, diameter or equivalent diameter are 0.1～10 μ m.
The moulding material advantage of the present invention's preparation is:
1. moulding and preparation method are simple, can be prepared into different shape;
2. can be directly as catalyst, again can be as catalyst carrier;
3. specific area height, the pore-size distribution that crushing strength height, degree of crystallinity height, porosity be big, possess different range;
4. do not contain additive, catalytic reaction activity, reaction rate height.
The specific embodiment
Mesopore titanium oxide whisker shaping material prepared in accordance with the present invention has excellent performance as the catalyst or the catalyst carrier of PETROLEUM PROCESSING, according to embodiment the present invention is further described below:
Embodiment 1.
With meso-porous titanium oxide whisker, titanium oxide sol is raw material, and wherein the meso-porous titanium oxide whisker is 80% (wt), and titanium oxide sol is 20% (wt), after the adding suitable quantity of water is fully mixed, through the banded extruder extruded moulding, puts into 400 ℃ of roastings of Muffle furnace after the drying.The moulding material that obtains is a strip, and equivalent diameter is 2mm, and degree of crystallinity is 45%, and specific area is 132m
2/ g, crushing strength is 0.54MPa, and porosity is 77%, and pore volume is 0.67cm
3/ g, the pore-size distribution peak can lay respectively at 5.5nm in several positions, 55nm and 7.6 μ m.
Other embodiment see Table 1.
The prescription of table 1. embodiment 2 ~ 7, preparation condition and performance
| Other embodiment | Form (wt) | Shape and equivalent diameter | Sintering temperature | Degree of crystallinity | Specific area m 2/g | Crushing strength MPa | Porosity % and pore volume cm 3/g | The pore-size distribution peak can several positions |
| Embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 | Mesoporous Ti0 2(w) 70% 2TiK (w), 30% mesoporous TiO 2(w) 60% anatase TiO 2(p) 35% 6TiK (w), 5% mesoporous TiO 2(w) 50% hydrolysis TiO 2 40％ 4TiK·2H 2O (w) 10% mesoporous TiO 2(w)40％ H 2Ti 2O 5(p)10％ TiO 2Colloidal sol 50% mesoporous TiO 2(w)20％ H 2Ti 8O 17·1.5H 2O (w) 25% hydrolysis TiO 250% metatitanic acid, 5% mesoporous TiO 2(w)5％ TiO 2Colloidal sol 90% anatase TiO 2(w) 5％ | Spherical 2.8mm granulated 0.3mm sheet 4mm annular 6.5mm multiple edge body shape 3.5mm strip 0.5mm | 300 ℃ 450 ℃ 600 ℃ 550 ℃ 500 ℃ 700 ℃ | 23％ 58％ 87％ 79％ 71％ 94％ | 174 125 54 82 117 32 | 0.45 0.76 2.12 1.77 1.58 2.83 | 72％ 0.62 63％ 0.45 59％ 0.39 47％ 0.34 38％ 0.28 30％ 0.13 | 4.5nm 9.2μm 6nm 60nm 5.3μm 9.3nm 17nm 9nm 23nm 4.8μm 8.7nm 43nm 1.8μm 10nm 12nm 0.3μm |
Illustrate: p represents particle, and w represents whisker; 2TiK represents two potassium titanates, and 6TiK represents six potassium titanates, and 4TiK represents potassium tetratitanate
Comparative example 1.
Do not add the meso-porous titanium oxide whisker, be raw material directly with common anatase titanium oxide whisker and titanium oxide sol, wherein common anatase titanium oxide whisker is 80% (wt), titanium oxide sol is 20% (wt), moulding material degree of crystallinity according to the preparation of the method for embodiment 1 is 13% only, is 1/4～1/3 of embodiment 1; Specific area is 22m
2/ g is 1/6 of embodiment 1; Do not have regular orderly nanostructured, SEAD is indicated as polycrystalline structure; Only there is a 20 ~ 80nm in while, is centered close to the pore-size distribution peak of 60nm.
Comparative example 2.
With meso-porous titanium oxide whisker, SiO
2Colloidal sol and 6TiK whisker are raw material, and wherein the meso-porous titanium oxide whisker is 60% (wt), SiO
2Colloidal sol is 35% (wt), and the 6TiK whisker is 5% (wt), according to embodiment 3 method shaping and roastings.The moulding material porosity of preparation only is 23%, is 1/3 of embodiment 3.
Comparative example 3.
Sintering temperature is elevated to 800 ℃, and other are with embodiment 4, and the specific area of the moulding material of preparation only is 23m
2/ g, porosity is reduced to 17%, all has only 1/3～1/2 of embodiment 4; And only existing can the pore-size distribution of several peak positions in about 0.4 μ m.
Comparative example 4.
Sintering temperature is 200 ℃, and other are with embodiment 5, and the moulding material degree of crystallinity of preparation is 11%, far below embodiment 5; Crushing strength is 0.14MPa only, has only 1/12 of embodiment 5, is difficult to the reaction system of certain pressure.
Comparative example 5.
With meso-porous titanium oxide whisker, methylcellulose is raw material, and according to embodiment 7 moulding, wherein the meso-porous titanium oxide whisker is 97% (wt), and the binding agent methylcellulose is 3% (wt), and specific area has only 18m after 700 ℃ of roastings
2/ g, crushing strength only are 0.25MPa, all far below embodiment 7.
By embodiment and comparative example as can be seen, the mesopore titanium oxide whisker shaping material of the present invention's preparation is outstanding in degree of crystallinity, specific area, crushing strength, porosity and aspect combination property advantages such as pore volume, pore-size distribution.The present invention can form and the preparation method by regulating raw material, obtains the meso-porous titanium oxide whisker preformed catalyst of function admirable; And because technology is simple, cost is lower, can be by large-scale production and extensive use.
List of references
[1] Jiang Zhigang, Zhang Shuguang, Li Yonggang, Xu Yafei, the manufacture method of TiO 2-based catalyst carrier, ZL01128861.2,2001; Y.Tadahiro, K.Midori, K.Shigefumi, Inorganic CobaltAdsorbent and its Production, JP61138530,1986.
[2] all dimensions of this Robert of Qiao Hansiansong Neil, titania extrudates, ZL90101299.8,1990.
[3] ShenBing Long, wheat is strong, and the Judd is wide etc., is hydro-dearsenic catalyst of carrier and preparation method thereof with titanium dioxide, ZL97118914.5,1997.
[4] D. Hai Nike, K. Haas, U. Lothar Staber that, the special Studdert of O. Hough, oxide catalyst, CN00122546.4,2000.
[5]T.Yasuhiro，N.Atsushi，O.Yukiyoshi，N.Hironao，Catalyst for PurifyingExhaust Gas，JP61245843，1986；S.Yuujirou，M.Tetsuo，M.Masashi，S.Masao，W.Hirobumi，Titanium Oxide Catalyst Carrier Mold Product and Manufacturethereof，JP53095892，1978；Y.Ryoji，Photocatalyst Composition，Forming Agentthereof and Base Body with Deposition of Photocatalyst Composition，JP10165811，1998.
[6]Y.Naomi，Catalyst for Removing Nitrogen 0xide and Production thereof，JP5154350，1993；Y.Yukio，K.Toshihiko，Production of Catalyst Base Plate，JP6007682，1994；I.Katsura，K.Hiroyuki，N.Kazuyoshi，M.Yutaka，Moisture-Permeable Aqueous Inorganic Coatings Having Good Antisoiling Property，JP2003206434，2003.
[7]K.Tesuo，Production of Catalyst for Hydrogenation of Hydrocarbon Oil，JP4156949，1992；M.Kunichi，S.Hikaru，O.Kazuhiko，Molded Titanium OxideProduct Useful as Catalyst Carrier，JP52016507，1977.
[8]D.J.Theodorus，S.Hennie，V.V.J.A.Robert，Titania Extrudates，GR3026117T，1998；D.J.Theodorus，S.Hennie，Titania Extrudates，CA2012663，1990；D.J.Theodorus，S.Hennie，V.V.J.A.Robert，Titania Extrudates asCatalyst Supports for Hydrocarbon Conversion，EP389041，1990.
[9] T Xi Mansiji; The SA rowland is many; DM Gao Fu etc., TiO 2-based catalyst carrier, ZL95193331.0,1995.
[10] M.He, X.Lu, X.Feng, L.Yu, Z.Yang, A simple approach to mesoporous fibroustitania from potassium dititanate[J] .Chem.Comm., 2004,2202; Lu Xiaohua, He Ming, Yang Zhuhong, Feng Xin, Zheng Zhong, sudden and violent peaceful clock, a kind of titanium oxide synthetic method of high-specific surface area, ZL03158274.5,2005.[11] N.Bao, X.Lu, X.Ji, X.Feng, J.Xie, Thermodynamic modeling and experimentalverification For ion-exchange synthesis of K
2O6TiO
2And TiO
2Fibers fromK
2O4TiO
2[J] .Fluid Phase Equilibr, 2002,193 (1-2), 229; M.He, X.Feng, X.Lu, et al., The application of ion-exchange model for the synthesis of derivativesof K
2Ti
4O
9Fiber[J] .J Chem Eng Jap, 2003,36 (10), 1259; M.He, X.Feng, X.Lu, et al., A controllable approach for the synthesis of titanate derivatives ofpotassium tetratitanate fiber[J] .J Mater Sci, 2004,39,3745.
Claims (8)
1, a kind of preparation method of mesopore titanium oxide whisker shaping material, it is characterized in that with one or more mixture and the meso-porous titanium oxide whisker in potassium titanate or derivatives thereof or other titanium oxide be raw material, make after moulding, 300 ℃～700 ℃ roastings, meso-porous titanium oxide whisker weight percent content is 5～80.
2, preparation method according to claim 1 is characterized in that moulding material degree of crystallinity＞20%, and specific area is 30～180m
2/ g, crushing strength is 0.4～3MPa, and porosity is 30～80%, and pore volume is 0.1～0.7cm
3/ g has at least two kinds in following three kinds of aperture features distributions, and first feature is distributed as 4～10nm, and second feature is distributed as 10～100nm, and the 3rd feature is distributed as 0.1～10 μ m.
3, preparation method according to claim 1 is characterized in that its equivalent diameter of moulding material is greater than 0.2mm.
4, preparation method according to claim 1 is characterized in that potassium titanate is one or more the mixture in two potassium titanates, potassium tetratitanate, six potassium titanates, eight potassium titanate particles or the whisker.
5, preparation method according to claim 1 is characterized in that the potassium titanate derivative is the potassium titanate that contains after the crystallization water or the ion-exchange.
6, preparation method according to claim 1 is characterized in that other titanium oxide are one or more the mixture in the amorphous compound of Detitanium-ore-type phase oxidation titanium whisker or particle or titanium.
7, preparation method according to claim 6, the amorphous compound that it is characterized in that titanium is for by the titanium oxide of sol-gel preparation or one or more the mixture in metatitanic acid or the hydrolysis oxidation titanium.
8, preparation method according to claim 1, the specific area that it is characterized in that the meso-porous titanium oxide whisker is greater than 50m
2/ g, diameter or equivalent diameter are 0.1～10 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100388633A CN100421783C (en) | 2006-03-15 | 2006-03-15 | Preparation method of mesopore titanium oxide whisker shaping material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100388633A CN100421783C (en) | 2006-03-15 | 2006-03-15 | Preparation method of mesopore titanium oxide whisker shaping material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1830548A true CN1830548A (en) | 2006-09-13 |
| CN100421783C CN100421783C (en) | 2008-10-01 |
Family
ID=36993139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100388633A Active CN100421783C (en) | 2006-03-15 | 2006-03-15 | Preparation method of mesopore titanium oxide whisker shaping material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100421783C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009018700A1 (en) * | 2007-08-07 | 2009-02-12 | Nanjing University Of Technology | A method for quick preparing titanium oxide or precursor thereof with a controllable structure from micropore to mesopore |
| CN102225783A (en) * | 2011-05-30 | 2011-10-26 | 南京钛威科技有限公司 | Preparation method of macroporous titanium oxide or precursor of macroporous titanium oxide |
| CN103806087A (en) * | 2014-02-27 | 2014-05-21 | 南京大学医学院附属鼓楼医院 | Preparation method for novel TiO2 nano crystal whisker materials commonly-loaded with gambogic acid |
| CN110935460A (en) * | 2018-09-21 | 2020-03-31 | 中国石油天然气股份有限公司 | High-selectivity hydrodesulfurization catalyst and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4012479A1 (en) * | 1990-04-19 | 1991-10-24 | Degussa | Titanium dioxide pellets, process for their preparation and their use |
| JP3076844B1 (en) * | 1999-07-19 | 2000-08-14 | 工業技術院長 | Mesoporous titanium oxide porous body and method for producing the same |
| CN100588618C (en) * | 2004-07-05 | 2010-02-10 | 华东理工大学 | Method for preparing titanium dioxide mesoporous material |
| CN1594102A (en) * | 2004-07-05 | 2005-03-16 | 华东理工大学 | Method for preparing titanium dioxide mesoporous material |
| RU2291839C2 (en) * | 2004-11-10 | 2007-01-20 | Институт Физической Химии Им. Л.В. Писаржевского Национальной Академии Наук Украины | Method and the semi-product used for production of the meso-porous titanium dioxide |
-
2006
- 2006-03-15 CN CNB2006100388633A patent/CN100421783C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009018700A1 (en) * | 2007-08-07 | 2009-02-12 | Nanjing University Of Technology | A method for quick preparing titanium oxide or precursor thereof with a controllable structure from micropore to mesopore |
| CN102225783A (en) * | 2011-05-30 | 2011-10-26 | 南京钛威科技有限公司 | Preparation method of macroporous titanium oxide or precursor of macroporous titanium oxide |
| CN103806087A (en) * | 2014-02-27 | 2014-05-21 | 南京大学医学院附属鼓楼医院 | Preparation method for novel TiO2 nano crystal whisker materials commonly-loaded with gambogic acid |
| CN103806087B (en) * | 2014-02-27 | 2016-07-06 | 南京大学医学院附属鼓楼医院 | A kind of new Ti O carrying gamlogic acid altogether2The preparation method of nano crystal whisker material |
| CN110935460A (en) * | 2018-09-21 | 2020-03-31 | 中国石油天然气股份有限公司 | High-selectivity hydrodesulfurization catalyst and preparation method thereof |
| CN110935460B (en) * | 2018-09-21 | 2023-02-28 | 中国石油天然气股份有限公司 | High-selectivity hydrodesulfurization catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100421783C (en) | 2008-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10751700B2 (en) | Nanostructured binary oxide TiO2/AI2O3 with stabilized acidity as catalytic support and its synthesis process | |
| EP1984301B1 (en) | Zirconium hydroxide | |
| CN1206025C (en) | Synthesis of titania with high specific surface area | |
| CN1287878A (en) | Process for preparing mesopore titania photocatalyst | |
| CN1830548A (en) | Preparation method of mesopore titanium oxide whisker shaping material | |
| CN113830826A (en) | Method for preparing shell-core structure mesoporous quantum titanium oxide by precipitation-self-assembly method | |
| EP2679542A1 (en) | Nanostrutured titania semiconductor material and its production process | |
| CN1752016A (en) | A kind of novel nano-titanium dioxide powder preparation method | |
| CN111659369B (en) | Preparation method of porous titanium dioxide/silicon dioxide/carbon nano composite material | |
| CN1974000A (en) | Method of preparing C-doped porous nanometer TiO2 photocatalyst with egg shell membrane as template | |
| CN1765511A (en) | PH adjusting hydrothermal preparation method of active nano crystal mesoporous titanium dioxide photocatalytic material | |
| CN101857267B (en) | Preparation method of titanium dioxide nano material with core-shell structure | |
| CN103801346B (en) | A kind of method preparing hydrotreating catalyst | |
| CN101045543A (en) | Method for preparing sheet alumina using coal series kaolin rock or flyash as raw material | |
| CN103801312A (en) | Preparation method for hydrotreatment catalyst | |
| CN1824382A (en) | Preparation method of titanium dioxide hollow microsphere | |
| EP2778135A1 (en) | Fibrous im-5 molecular sieve and preparation process thereof | |
| CN1363521A (en) | Process for preparing anatase crystal type nano TiO2 | |
| CN113979471B (en) | Synthetic method of rutile type titanium dioxide nano-composite | |
| CN114956167A (en) | Nano titanium dioxide with ultrahigh specific surface area and preparation method thereof | |
| CN1506311A (en) | Prepn process of nano level rutile-type titania powder | |
| KR100664751B1 (en) | Preparation of titania nanotubes | |
| CN113559888B (en) | Modified vulcanized hydrogenation catalyst, and preparation method and application thereof | |
| CN1095689C (en) | Process for preparing aluminium oxide-titanium oxide bicomponent | |
| Shao et al. | Sol-gel synthesis of less expensive mesoporous titania-tin dioxide systems: Investigation of the influence of tin dioxide on the phase structure, morphology and optical properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |